This invention pertains to oligomeric polysulfones and, more particularly, to normally solid polyarylene polyether polysulfone thermoplastic resins obtained by extension of oligomeric polysulfone with carbonates, esters, ethers or silyl ether linkages.
Polyarylene polyether polysulfone thermoplastic resins constitute a family of tough, rigid, high-strength thermoplastics which maintain their properties over a temperature range from -150.degree. F. (-101.degree. C.) to above 300.degree. F. (149.degree. C.). These polysulfone resins can be prepared by a substantially equimolar one-step reaction of a double alkali metal salt of a dihydric phenol with a dihalobenzenenoid compound in the presence of specific liquid organic sulfoxide or sulfone solvents under substantially anhydrous conditions using an azeotroping solvent, such as, chlorobenzene. They may also be prepared by Friedel-Crafts reactions in which sulphone linkages are formed by reaction of aryl sulphonyl chlorides with aromatic nuclei as well as by a monosalt process as disclosed by ICI in British Pat. No. 1,016,245.
The preferred polysulfones are prepared by the first method and a particularly preferred resin is one composed of repeating units having the structure shown below: ##STR1## wherein n=about 10 to about 500. This is commercially available from Union Carbide Corporation as UDEL Polysulfone P-1700. For the synthesis of this resin the dihydric phenol is bisphenol A, i.e., 2,2-bis(p-hydroxyphenyl) propane. Other dihydric phenols which can be used include the following: 2,2-bis-(4-hydroxyphenyl)propane, 2,4-dihydroxydiphenylmethane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)ethane, 1,2-bis-(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis-(3-methyl-4-hydroxyphenyl)ethane, 1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(2-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(4-hydroxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pentane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis-(4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis-(4-hydroxyphenyl)-1,2-bis-(phenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-1-phenyl-propane and the like;
Di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, 5'-chloro-2,4'-dihydroxydiphenyl sulfone, 5'-chloro-4,4'-dihydroxydiphenyl sulfone and the like;
Di(hydroxyphenyl) ethers such as bis-(4-hydroxyphenyl)-ether, the 4,5'-, 4,2'-, 2,2'-, 2,3'-dihydroxydiphenyl ethers, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis-(4-hydroxy-3-isobutylphenyl)-ether, bis-(4-hydroxy-3-isopropylphenyl)-ether, bis-(4-hydroxy-3-chlorophenyl)ether, bis-(4-hydroxy-3-fluorophenyl)-ether, bis-(4-hydroxy-3-bromophenyl)-ether, bis-(4-hydroxynaphthyl)-ether, bis-(4-hydroxy-3-chloronaphthyl)-ether, bis-(2-hydroxydiphenyl)-ether, 4,4'-dihydroxy-2,6-dimethoxydiphenyl)ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl)ether, 4,4'-dihydroxydiphenyl and the like and mixtures thereof.
Also suitable are the bisphenol reaction products of 4-vinyl-cyclohexene and phenols, e.g., 1,3-bis(p-hydroxyphenyl)-1-ethylcyclohexane and the bisphenol reaction products of dipentene or its isomers and phenols such as 1,2-bis(p-hydroxyphenyl)-1-methyl-4-isopropylcyclohexane as well as bisphenols such as 1,3,3-trimethyl-1-(4-hydroxyphenyl)-6-hydroxyindane, and 2,4-bis-(4-hydroxyphenyl)-4-methylpentane, and the like.
Particularly desirable dihydric polynuclear phenols have the formula ##STR2## wherein Y is an alkyl having 1 to 4 carbon atoms r and s have values from 0 to 4 inclusive and R.sup.1 is a divalent saturated aliphatic hydrocarbon radical, particularly alkylene and alkylidene radicals having from 1 to 3 carbon atoms, and cycloalkylene radicals having up to and including 9 carbon atoms.
While polysulfone resins have found wide commercial use in molding and extrusion applications for the electronic, electrical, appliance, auto, aircraft and general industrial markets as well as adhesives because of their adhesion to hot metals, inherent high softening point and outstanding heat stability, their use has been hampered due to high cost of production. Part of this high cost has been attributed to the need for handling high polymer viscosity resins in filtration, extraction and solvent devolatilization operations which severely limit capacities and increases production cycles.
It is therefore an object of this invention to provide a more economical route to the production of polysulfone resins.
It is also an object of this invention to avoid formation of by-products which are difficult to remove or are deterious to the final polymer product.
Other objects will become apparent to those upon a further reading of the specification.